Branched primary alcohol compositions and derivatives thereof

ABSTRACT

A detergent composition having cold water solubility and exhibiting high calcium tolerance can be produced from biodegradable branched ether derivative compositions derived from a branched ether primary alcohol represented by the formula: 
                 
 
wherein R 1  represents hydrogen or a hydrocarbyl radical having from 1 to 3 carbon atoms, R 2  represents a hydrocarbyl radical having from 1 to 7 carbon atoms, x is a number ranging from 0 to 16, preferably from 3 to 13, wherein the total number of carbon atoms in the alcohol ranges from 9 to 24.

This is a division of application Ser. No. 10/025,080 filed Dec. 19,2001, the entire disclosure of which is hereby incorporated byreference, which claims the benefit of U.S. Provisional Application No.60/257,670 filed Dec. 21, 2000, the entire disclosure of which is herebyincorporated by reference.

FIELD OF INVENTION

This invention relates to a certain branched primary alcohol compositionuseful in producing detergent compositions.

BACKGROUND OF THE INVENTION

Nonionic and anionic surfactants are important constituents in manyapplications. Both aromatic and aliphatic sulfates and sulfonates are animportant group of anionic surface-active agents used extensively in anumber of industrial applications. These include operations in drillingfor and recovery of crude oil; emulsifiers for pesticides used in cropprotection; in shampoos and creams for personal care; bar soaps; laundrydetergents; dishwashing liquids, hard surface cleaners; emulsifiers foremulsion polymerization systems; lubricants; wetting agents; anddispersants in a variety of specialized industrial applications.

The surfactants used in cleaning applications are designed to remove awide variety of soils on fabrics and hard surfaces. Surfactants in thisapplication have a balance of particulate soil removal and grease andoily soil removal characteristics. Especially in detergent compositionsfor cleaning fabrics, the surfactants used should have the ability toremove a broad spectrum of soil types.

In many cases, however, a surfactant which exhibits high detergencypower will be poorly soluble in cold water. For example, surfactantspresent in laundry powder detergents should dissolve completely in arelatively short time interval under whatever wash temperature andagitation conditions are employed in the wash cycle chosen by theconsumer. Undissolved detergent not only fails to provide cleaningbenefits, but also may become entrapped in the laundry articles andremain behind as a residue either in the machine or on the garmentsthemselves. The problem of dispersion and solubilization in the washcycle are made worse under conditions of cold water washing especiallyat or below about 50° F. (10° C.). Lower wash temperatures are becomingever increasing factors in today's wash loads as both energyconservation and increased use of highly colored, delicate fabrics leadto wash conditions that make powders difficult to dissolve.

In contrast to nonionic surfactants, which exhibit inverse solubilitybehavior and which, by virtue of hydrogen bridge bonds, show bettersolubility in cold water than in warm water, anionic surfactants showconventional behavior, i.e. their solubility increases more or lesslinearly with the temperature until the solubilized product is reached.The surfactant employed, whether anionic or nonionic, should be designedto remain homogeneous in the wash media at cold water washingtemperatures to optimize the cleaning performance of the surfactant.Accordingly, surfactants with the ability to remove sebum types of soiland which have low Krafft point temperatures are desirable.

Surfactants which have good washing and cleaning performance have lowKrafft temperatures. The Krafft temperature refers to the temperature atwhich the solubility of an anionic surfactant undergoes a sharp,discontinuous increase with increasing temperature. The solubility of ananionic surfactant will increase slowly with an increase in temperatureup to the temperature point at which the solubility exhibits anextremely sharp rise. The temperature corresponding to the sharp rise insolubility is the Krafft temperature of anionic surfactant. At atemperature approximately 4° C. above the Krafft temperature, a solutionof almost any composition becomes a homogeneous phase. Further, theKrafft temperature is a useful indicator of detergency performancebecause at and above the Krafft temperature, surfactants begin to formmicelles instead of precipitates, and below the Krafft temperaturepoint, surfactants are insoluble and form precipitates. At the Krafftpoint temperature, the solubility of a surfactant becomes equal to itscritical micelle concentration, or CMC. The appearance and developmentof micelles are important since certain surfactant properties such asfoam production depend on the formation of these aggregates in solution.

Each type of surfactant will have its own characteristic Kraffttemperature point. In general, the Krafft temperature of a surfactantwill vary with the structure and chain length of the hydrophobichydrocarbyl group and hydrophilic portion of the molecule. Kraffttemperature for ionic surfactants is, in general, known in the art. See,for example, Myers, Drew, Surfactant Science and Technology, pp. 82-85,VCH Publishers, Inc. (New York, N.Y., USA), 1988 (ISBN 0-89573-399-0),and K. Shinoda in the text “Principles of Solution and Solubility”,translation in collaboration with Paul Becher, published by MarcelDekker, Inc. 1978 at pages 160-161, each of which is incorporated byreference herein in its entirety.

A surfactant which exhibits a high Krafft point is generallyinsufficient in detergency and foaming power. Since the Krafft point isa factor having an influence on the surface activating capacities of asurfactant, at temperatures lower than the Krafft point,surface-activating capacities such as detergency, foaming power andemulsifying power begin to deteriorate, and the surfactant mayprecipitates on the fabric. Thus, the surfactant should desirablypossess a low Krafft point, especially in light of current performancerequirements in cold water washing temperatures.

However, even surfactants with good detergency and high cold watersolubility limits, as shown by their low Krafft point temperatures, maynevertheless leave behind precipitates on the surface to be cleaned ifthe surfactant is not tolerant to the concentration of electrolytes(typically magnesium and calcium) present in the aqueous washing medium.The electrolyte of most concern in wash water is calcium due to its highconcentration in many aqueous media and its ability to exchange with thesoluble sodium cation on sulfated surfactants to form an insolublecalcium salt of the sulfated surfactant, which precipitates out onto thesubstrate to be cleaned as a particle or film. The hardness of thewater, or concentration of calcium and other electrolytes in water, willvary widely depending on the purification method and efficiency of watertreatment plants which dispense water to the consumer of the detergentor cleaning composition. Accordingly, there remains a need to provide asurfactant which is tolerant to high concentrations of calcium so as toprovide a cleanser which performs as expected in a wide variety ofaqueous media.

Due to constraints on water consumption, especially in locations wherethe supply of drinking water to a population is limited, inadequate, orexpensive, there is a desire to employ unprocessed or lightly processedwater having a high concentration of saline as a wash media. Inparticular, there exists a need in some locations to use sea water orbrackish water which is unprocessed or lightly processed as the aqueousmedia for many applications outside of drinking water, such asdishwashing and laundry water. The need to provide for a surfactantwhich is tolerant to high concentrations of electrolytes, such ascalcium, is readily apparent if one must wash or clean a substrate insea water or brackish water. Thus, there also exists a desire to find asurfactant composition, which is so highly tolerant to calcium that itis suitable for use in seawater or brackish as a cleansing agent.

It would also be desirable to manufacture a surfactant which can beeasily and economically stored and transported. Polyoxyethylene nonioniclinear alcohol surfactants, especially those containing from 3 or moreethylene oxide units, are solid or waxy products at ambient conditions(25° C. and 1 atm). Since these waxy or solid products cannot be pumpedat ambient conditions, they must first be melted into the liquid phaseand kept as a liquid during offloading and feeding into a reactionvessel or a blend tank. Further, the waxy and solid polyoxyethylenelinear alcohols must be shipped and/or transported in drums, which takeup more warehouse space than liquid storage tanks. It would be desirableto produce a polyoxyalkylene surfactant which is flowable and pumpableat ambient conditions, and yet more desirable to produce such ansurfactant which is flowable and pumpable in cold climates wheretemperatures drop to 0° C.

SUMMARY OF THE INVENTION

A branched primary alcohol composition is provided comprising a branchedether primary alcohol represented by the formula

wherein R₁ represents hydrogen or a hydrocarbyl radical having from 1 to3 carbon atoms, R₂ represents a hydrocarbyl radical having from 1 to 7carbon atoms, x is a number ranging from 0 to 16, wherein the totalnumber of carbon atoms in the alcohol ranges from 9 to 24.

There is also provided derivatives of the branched primary alcoholcompositions such as alkoxylates, sulfates, and alkoxylsulfates of suchalcohol compositions. The derivatives are useful as detergentcompositions having cold water solubility and high tolerance to calcium.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

It has now been found that a surfactant and a composition exhibitinghigh calcium tolerance can be provided using the composition of theinvention containing derivatives of certain branched primary alcohol. Ithas been further found that the product has better cold water solubilitythan a linear alkyl sulfate having a comparable carbon number asmeasured by its Krafft point.

There is now provided a certain branched primary alcohol sulfatecomposition and a certain branched primary alcohol alkoxylsulfatecomposition having a calcium tolerance of 5000 ppm CaCl₂ or more, and asmuch as 50,000 or more, preferably, 20,000 CaCl₂ or more, morepreferably 50,000 ppm or more, most preferably surfactant and acomposition which possesses high calcium tolerance.

There is also provided a branched ether primary alcohol having a remotealpha branch ether trimethylene group, derivatives thereof such asalkoxylates (e.g., ethoxylates and/or propoxylates), the sulfates ofeach, and biodegradable branched ether surfactant compositions. Theremote alpha branch ether trimethylene moiety is structurallyrepresented as:

wherein R₂ represents a hydrocarbyl radical having from 1 to 7 carbonatoms, preferably 1 carbon atom.

The term “hydrocarbyl” as used herein means that the radical concernedis primarily composed of hydrogen and carbon atoms but does not excludethe presence of other atoms or groups in a proportion insufficient todetract from the substantially hydrocarbon characteristics of theradical concerned. Such radicals include:

-   -   (i) Hydrocarbon groups, for example, aliphatic (e.g., alkyl or        alkenyl), alicyclic (e.g., cycloalkyl or cycloalkenyl) and        aromatic groups, aromatic groups having aliphatic or alicyclic        substituents, and aliphatic and alicyclic groups having aromatic        substituents. Examples of hydrocarbon groups include methyl,        ethyl, ethenyl, propyl, propenyl, butenyl, cyclohexyl,        t-butylphenyl, 2-benzethyl and phenyl groups;    -   (ii) Substituted hydrocarbon groups, that is, groups having one        or more non-hydrocarbon substituents which do not detract from        the substantially hydrocarbon characteristics of the group.        Examples of suitable non-hydrocarbon substituents include        hydroxy, nitrile, nitro, oxo, chloro groups, and groups having        ether or thioether linkages; and    -   (iii) Hetero groups, that is, groups containing an atom other        than carbon in a chain or ring otherwise composed of carbon        atoms, the said atom not detracting from the substantially        hydrocarbon characteristics of the group and inert to reactions.

Nitrogen, oxygen and sulphur may be mentioned as suitable hetero atoms.The hydrocarbyl radicals preferably contain only one non-hydrocarbonsubstituent or one non-carbon hetero atom if such substituents or atomsare present.

Anionic surfactants in detergent formulations are generally known to besubject to precipitation from wash water solutions containing hard waterions, e.g., magnesium and particularly calcium. Without intending to bebound by the theory, it is believed that the tolerance of the surfactantmolecules of the invention, the compositions containing these molecules,and the formulations thereof, to calcium ions in wash solutions isattributable to the unique structure of the branched primary alcoholhaving a remote alpha branch ether trimethylene group.

The certain branched primary alcohol composition of the invention isrepresented by the formula:

wherein R₁ represent hydrogen or a hydrocarbyl radical having from 1 to3 carbon atoms, preferably hydrogen, R₂ represents a hydrocarbyl radicalhaving from 1 to 7 carbon atoms, preferably 1 carbon atom, x is a numberranging from 0 to 16, preferably from 3 to 13, wherein the total numberof carbon atoms in the alcohol ranges from 9 to 24, preferably from 9 to20.

The branched ether surfactant of the invention is made by reacting anolefin with 1,3-propane diol in the presence of a suitable catalystunder primary alcohol forming conditions.

An olefin means any compound containing at least one carbon-carbondouble bond. The desired average chain length of the olefin ranges from3-18 aliphatic carbon atoms, preferably from 6-18, and more preferablyfrom 12-16 aliphatic carbon since molecules within this range are usedin many washing applications. The most suitable chain length, however,will depend upon the particular end use, such as dish washing, liquidhand soap, bar soap, laundry detergent, hard surface cleaners, or oilfield applications.

The olefins may be linear or branched, may contain multiple double bondsanywhere along the chain, and may also contain acetylenic unsaturation.Further, the olefins may be substituted or unsubstituted, or may containheteroatoms. The olefin may also be a bridged alpha olefin, such as aC₁-C₉ alkyl substituted norbornenes. Examples of norbornenes include5-methyl-2-norbornene, 5-ethyl-2-norbornene, and5-(2′-ethylhexyl)-2-norbornene.

The olefin may contain an aryl, alkaryl, or cycloaliphatic group alongwith an aliphatic moiety within the same olefin compound, or the olefinmay consist solely of an aliphatic compound. Examples of aryl groupsinclude phenyl, naphthyl, and the like. Examples of cycloaliphaticmoieties include the cyclo propyls, butyls, hexyls, octyls, decyls, etc.Examples of alkaryls include tolyl, xylyl, ethylphenyl, diethylphenyl,and ethylnaphthyl. Preferably, the olefin composition comprises at least90 wt. %, more preferably at least 95%, most preferably at least 98 wt.% aliphatic compounds.

The olefin may contain branched or linear olefins, or both. Examples ofbranching include alkyl, aryl, or alicyclic branches, preferably alkylbranches, and especially those alkyl groups having from 1 to 4 carbonatoms. The location of a branch on the olefin is not limited. Branchesor functional groups may be located on the double bond carbon atoms, oncarbon atoms adjacent to the double bond carbon atoms, or anywhere elsealong the carbon backbone.

The number of unsaturated bond sites along the chain is also notlimited. The olefin may be a mono-, di-, tri-, etc. unsaturated olefin,optionally conjugated. The olefin may also contain acetylenicunsaturation. Preferably, the olefin composition comprises at least 90wt. %, more preferably at least 95 wt. %, most preferably at least 98wt. % mono-unsaturated olefin.

The olefin composition may comprise alpha olefins or internal olefins.An alpha olefin is an olefin whose double bond is located on both of aand P carbon atoms. An a carbon atom is any terminal carbon atom,regardless of how long the chain is relative to other chain lengths in amolecule. Specific non-limiting examples of alpha olefins suitable foruse in the invention include 1-propylene, 1-butene, 1-pentene,1-isopentene, 1-hexene, 2-methyl-1-hexene, 1-octene, 1-nonene, 1-decene,1-undecene, 1-dodecene.

An internal olefin(s) is an olefin whose double bond is located anywherealong the carbon chain except at any terminal carbon atom.

The olefin composition feedstock is generally produced by commercialprocesses such as the oligomerization of ethylene, optionally followedby isomerization and disproportionation, such as those manufactured byShell Chemical Company under the trademark NEODENE, or thosemanufactured by Chevron Chemical Company and BP-Amoco. Specificprocedures for preparing suitable linear olefins from ethylene aredescribed in U.S. Pat. Nos. 3,676,523, 3,686,351, 3,737,475, 3,825,615and 4,020,121, the teachings of which are incorporated herein byreference. While most of such olefin products are comprised largely ofalpha-olefins, higher linear internal olefins are also commerciallyproduced, for example, by the chlorination dehydrochlorination ofparaffins, by paraffin dehydrogenation, and by isomerization ofalpha-olefins. Linear internal olefin products in the C6 to C18 rangeare marketed by Shell Chemical Company and by Chevron Company.

Alternatively, the olefin composition may be produced by theFischer-Tropsch process, which typically contains a high proportion ofparaffins. A Fischer-Tropsch process catalytically hydrogenates CO toproduce compositions containing aliphatic molecular chains. Otherprocesses for making feedstocks which may contain mixtures of olefinsand paraffins include the dehydrogenation of paraffin, such as thosemade by the Pacol™ processes of UOP, and the cracking of paraffin waxes.

The olefin feedstock composition may be a processed stream that has beenfractionated and/or purified by a conventional distillation, extraction,or other separation operation to obtain a desired carbon number cut.Such operation produce compositions containing a mixture of carbonnumbers or a single carbon cut composition. In these feedstocks, amixture of olefins having different carbon numbers within the statedrange and outside of the stated range may be present. However, theaverage carbon number of the mixture of all olefins is within the statedrange. The feedstock stream preferably contains an average aliphaticcarbon number ranging from C₆-C₁₆, and more preferably ranging fromC₁₂-C₁₆, and wherein the predominant olefin species is within theseranges, inclusive. In addition to mixtures of olefins within this range,one may also employ what are known as single carbon cuts of olefins asfeedstocks, wherein the single cut is within this range. For example,the feedstock employed may be a single C₆, C₈, C₉, C₁₀, C₁₁, C₁₂, C₁₄,or C₁₆ carbon cut.

The most preferred olefin composition feedstock are those obtained fromethylene oligomerization and Fischer-Tropsch (FT) synthesis. In oneembodiment, the feedstock used comprises an alpha olefin compositionhaving at least 70 wt. % or more, more preferably at least 80 wt. % ormore, most preferably at least 90 wt. % or more, of linear alphamono-olefins within the desired carbon number range, (e.g., C₆, C₉₋₁₁,C₁₁₋₁₅, C₁₄₋₁₅, C₁₅₋₁₈, etc.), the remainder of the product being olefinof other carbon number or carbon structure, diolefins, paraffins,aromatics, and other impurities resulting from the synthesis process.

The catalyst used in the synthesis of the branched ether primary alcoholis preferably an acid catalyst. The acid catalyst is any conventionalacidic catalyst effective to catalyze the reaction of the olefin withthe diol to produce the branched alcohol surfactant of the invention.Conventional acidic catalysts include, broadly, the Bronsted acids,Lewis acids or Friedel-Crafts catalysts, zeolites, and ionic exchangeresins. The catalyst may be homogeneous or heterogeneous in the reactionmixture of olefin, diol, and reaction product. The reactants may contacta heterogeneous catalyst in suspension or on a fixed bed.

Suitable Lewis Acids typically include the halides and alkyl compoundsof the elements in Groups IV B to XVIII B and III A to VI A of thePeriodic Table of the Elements. Examples of Lewis acids andFriedel-Crafts catalysts are the fluorides, chlorides, and bromides ofboron, antimony, tungsten, iron, nickel, zinc, tin, aluminum, gallium,indium, zirconium, vanadium, bismuth, titanium and molybdenum. The useof complexes of such halides with, for example, alcohols, ethers,carboxylic acids, and amines are also suitable. More specific examplesinclude BF₃, BCl₃, aluminum bromide, FeCl₃, SnCl₄, SbCl₅, AsF₅, AsF₃,TiCl₄, trimethyl aluminum, triethyl aluminum, and AlR[n]X[3-n]wherein nis an integer from 0 to 3, R is C1-C12 alkyl or aryl, and X is a halide,for example, Al(C₂H₅)₃, Al(C₂H₅)₂Cl, Al(C₂H₅)Cl₂, and AlCl₃, titaniumtetrachloride, zirconium tetrachloride, tin tetrachloride vanadiumtetrachloride and antimony pentafluoride.

Specific examples of Bronsted acids include, but are not limited to,phosphoric acid, sulfuric acid, sulfur trioxide, sulfonic acid, boricacid, hydrofluoric acid, fluorosulfonic acid, trifluoromethanesulfonicacid, and dihydroxyfluoroboric acid, perchloric acid and theperchlorates of magnesium, calcium, manganese, nickel and zinc; metalsoxalates, sulfates, phosphates, carboxylates and acetates; alkali metalfluoroborates, zinc titanate; and metal salts of benzene sulfonic acid.

Suitable organic sulfonic acids include the alkane- and cycloalkanesulfonic acids, as well as arenesulfonic acids and heterocyclic sulfonicacids. Specific examples of the alkane sulfonic acids includemethanesulfonic acid, ethanesulfonic acid, propanesulfonic acid,butanesulfonic acid, pentanesulfonic acid, hexanesulfonic acid,dodecanesulfonic acid, hexadecanesulfonic acid, trifluoromethanesulfonic acid, sulfosuccinic acid, and cyclohexylsulfonic acid. Specificexamples of arenesulfonic acids include benzenesulfonic acid,toluenesulfonic acid, styrene-(i.e., vinyl benzene) sulfonic acid,5-sulfosalicylic acid, phenolsulfonic acid, and 1,6-naphthalenedisulfonic acid. Specific examples of heterocyclic sulfonic acidsinclude sulfanilic acid. Alkyl and aryl groups of the sulfonic acidmolecule are suitably substituted with relatively inert organic and/orinorganic substituents. Examples of substituted organic sulfonic acidsinclude 4-hydroxybenzene sulfonic acid, trifluoromethane sulfonic acid,isethionic acid, and taurine.

A class of sulfur based acids commonly used in homogeneous acidiccatalyzed reactions include sulfuric acid, sulfur trioxide, C1 to C30alkyl sulfuric acids, sulfanilic acid, toluenesulfonic acid,styrenesulfonic acid, methanesulfonic acid, and 5-sulfosalicylic acid.

Also included as an acid catalyst are any of the alkoxylation catalysts,magnesium in combination with halides of aluminum, boron, zinc,titanium, silicon, or molybdenum; BF₃ or SiF₄ in combination with analkyl or alkoxide compound of aluminum, gallium, indium, thallium,titanium, zirconium and hafnium; and a mixture of HF and one or moremetal alkoxides.

Instead of an acidic homogeneous catalyst, one may also employ a solidacidic heterogeneous catalyst. Solid acidic catalysts include acidicpolymeric resins, supported acids, and acidic inorganic oxides. Thesolid acidic catalysts have the advantage of avoiding the difficultseparation steps for removing the catalyst from unreacted diol in theproduct mixture, and further avoid the need to deactivate the catalystin the event that the catalyst is not removed from the product mixture.In one embodiment of the invention, the diol is pretreated to reduce thequantity of carbonyl compounds present as impurities in the diolcomposition prior to reaction with the olefin in the presence of a solidacidic heterogeneous catalyst, thereby extending the life of the solidacidic catalyst. Typical carbonyl impurities present in a diol includealdehydes or acetals. One example of a suitable pre-treatment is tohydrotreate the diol. Suitable hydrotreating methods include treatmentwith sodium borohydride or catalytic hydrogenation such as nickel onalumina or silica catalyst. In a more preferred embodiment, the amountof carbonyl impurities present in the diol is reduced to less than 100ppm, more preferably to less than 50 ppm, most preferably to less than10 ppm.

An example of a solid acidic polymeric resin is a solid acidic ionexchanger having acid active sites and a strong acid activity of eachacid site. Common acidic ion exchange resins are sulfated resins,wherein the resins are copolymers of styrene and divinylbenzene, phenolbased resins, poly(tetrafluoroethylene) polymers or siloxane polymers.Specific examples of such resins include the line of AMBERLYST®catalysts, including AMBERLYST® 15, 36 or 38, NAFION® or DELOXAN®catalysts. Other supported solid acidic catalysts include the Lewisacids (examples include BF₃, BCl₃, AlCl₃, AlBr₃, FeCl₂, FeCl₃, ZnCl₂,SbF₅, SbCl₅ and combinations of AlCl₃ and HCl) which are supported onsolids such as silica, alumina, silica-aluminas, zirconium oxide orclays. When supported liquid acids are employed, the supported catalystsare typically prepared by combining the desired liquid acid with thedesired support and drying. Supported catalysts which are prepared bycombining a phosphoric acid or sulfur based acid with a support are lowin cost.

Acidic inorganic oxides which are useful as catalysts include, but arenot limited to, aluminas, silica-aluminas, aluminophosphates, naturaland synthetic pillared clays, and natural and synthetic zeolites such asfaujasites, mordenites, L, omega, X, Y, beta, ZSM, and MCM zeolites.

Representative examples of naturally occurring zeolites includefaujasite, mordenite, zeolites of the chabazite-type such as erionite,offretite, gmelinite and ferrierite. Clay catalysts, another class ofcrystalline silicates, are hydrated aluminum silicates. Typical examplesof suitable clays, which are acid-treated to increase their activity,are made from halloysites, kaolinites and bentonites composed ofmontmorillonite. These catalysts can be synthesized by known methods andare commercially available.

Suitable synthetic zeolites include ZSM-4 as described in U.S. Pat. No.4,021,447, ZSM-5 as described in U.S. Pat. No. 3,702,886, ZSM-11 asdescribed in U.S. Pat. No. 3,709,979, ZSM-12 as described in U.S. Pat.Nos. 3,832,449 and 4,482,531, ZSM-18 as described in U.S. Pat. No.3,950,496, ZSM-20 as described in U.S. Pat. No. 3,972,983, ZSM-21 asdescribed in U.S. Pat. No. 4,046,859, ZSM-25 as described in U.S. Pat.No. 4,247,416, ZSM-34 as described in U.S. Pat. No. 4,086,186, ZSM-38 asdescribed in U.S. Pat. No. 4,046,859, ZSM-39 as described in U.S. Pat.No. 4,287,166 ZSM-43 as described in U.S. Pat. No. 4,247,728, ZSM-45 asdescribed in U.S. Pat. No. 4,495,303, ZSM-48 as described in U.S. Pat.No. 4,397,827, ZSM-50 as described in U.S. Pat. No. 4,640,829, ZSM-51 asdescribed in U.S. Pat. No. 4,568,654, ZSM-58 as described in U.S. Pat.No. 4,698,217, MCM-2 as described in U.S. Pat. No. 4,647,442, MCM-14 asdescribed in U.S. Pat. No. 4,619,818, MCM-22 as described in U.S. Pat.No. 4,954,325, MCM-36, MCM-49 as described U.S. Pat. No. 5,236,575,MCM-56, SSZ-25, SSZ-31, SSZ-33, SSZ-35, SSZ-36, SSZ-37, SSZ-41, SSZ-42,beta as described in U.S. Pat. No. 3,308,069 and RE. Pat. No. 28,341, Xas described in U.S. Pat. No. 3,058,805, Y as described in U.S. Pat. No.3,130,007, and mordenite as described in U.S. Pat. No. 3,996,337, theentire contents of which are incorporated herein by reference. Ifdesired, the zeolites can be incorporated into an inorganic oxide matrixmaterial such as a silica-alumina.

Representative examples of useful silica alumina phosphate catalystsinclude SAPO-5, SAPO-11 and SAPO41 as described in U.S. Pat. No.4,440,871, incorporated herein by reference.

Intermediate pore size (up to 7.5 Angstroms in the largest dimension atthe pore opening) and larger pore zeolites are preferred. Large poresize zeolites are most preferred because they can accommodate the largerolefin molecules, thereby providing a higher active surface area forreaction between the diols and olefins.

Examples of intermediate pore size zeolites include ZSM-5, ZSM-11,ZSM-12, ZSM-21, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM-48, ZSM-57, andZSM-58.

Larger pore size zeolites include MCM-22, zeolite Beta, zeolite Y,ZSM-20, and the like. Examples of a preferred modified Y type zeoliteinclude those disclosed in U.S. Pat. No. 5,059,567, which disclosure ishereby incorporated by reference.

Such zeolite catalyst should be at least partly in the acidic (H) formto confer the acidity for the reaction but may contain other cationssuch as ammonium (NH4⁺)

The form and the particle size of the catalyst are not critical to thepresent invention and may vary depending, for example, on the type ofreaction system employed. Non-limiting examples of the shapes of thecatalyst in the present invention include balls, pebbles, spheres,extrudates, channeled monoliths, honeycombed monoliths, microspheres,pellets, or structural shapes, such as lobes, trilobes, quadralobes,pills, cakes, honeycombs, powders, granules, and the like, formed usingconventional methods, such as extrusion or spray drying.

The diol and olefin react through the hydroxyl-double bond sites in thepresence of an acidic catalyst to produce a branched primary alcoholether surfactant of the invention containing within the molecule theremote alpha branch ether trimethylene moiety. For illustrativepurposes, when the olefin is an alpha-olefin, the reaction proceedsaccording to the following equation:

R₁ and R₂ represents the hydrocarbyl group as described above, and R₂′is R₂ less hydrogen where the linkage with the CH group is by doublebond and x is the same as described above. When the olefin is reactedwith the diol, the hydroxyl hydrogen becomes bonded to the R₂′ to becomeR₂.

The products produced from the reaction of the olefin and diolcompositions include the isomers of the olefin-diol adduct, olefindimers, diolefin ether adducts, and diol dimers. Isomers of theolefin-diol adduct are made by reaction of the diol at theelectropositive stable double bond carbon. In the presence of an acidiccatalyst, double bond isomerization may occur, resulting in an productmixture which contains branches of different carbon number lengthdepending upon the position of the double bond at the time the diolreacts with the olefin. To illustrate, the reaction of 1,3-propanediolwith 1-dodecene in the presence of an acidic catalyst may produce thefollowing isomers:

I₁ is made by the nucleophilic attack of the oxygen atom with an olefinwhen the double bond is in the alpha 1,2 carbon atom position. In thiscase, no double bond isomerization occurs, resulting in the desiredproduct. I₂ is made when the olefinic double bond is isomerized to the2,3 carbon atoms, and I₃ is made when the olefinic double bond isisomerized to the 3,4 carbon atoms. Double bond isomerization can beminimized by selection of an acidic catalyst which does not tend todouble bond isomerize the olefin. Double bond isomerization may also beminimized by reducing the residence time of the diol-olefin reaction,and by carrying out the diol-olefin reaction at temperatures higher thantypical temperatures favored for double bond isomerization. In general,double bond isomerization is favored at temperatures ranging from 50° C.to 150° C.

Another by-product, the diolefin ether adduct, is made when two olefinmolecules react with diol across the diol hydroxyl groups. Toillustrate, such a by-product is represented by the formula:

wherein R₁, R₂, and x is as described above. Formation of thisby-product is minimized by using a molar excess of propanediol toolefins. While suitable molar ratios of diol to olefin range from 0.1:1to 100:1, it is preferred to use a diol to olefin ratio of at least 1:1,more preferably from greater than 1:1, and most preferably at least1.5:1. An alternative which simulates a molar excess of diol to olefinto obtain the same effect, the olefin may be slowly added over a periodof time to the whole amount of diol to be reacted over a period to thediol to the olefin/catalyst mixture, having the effect of a large molarexcess of diol.

Other by products which may be formed in the reaction of an olefin witha diol include the dimers of the olefins contained in the olefincomposition, the dimers of the diols used in the diol composition.

The olefin-diol adducts of the invention are obtained in high purity.Based on the weight percentage of reaction products, the reaction of theolefin with diol in the presence of an acid catalyst, the selectivity ofthe olefin-diol product is 80 wt. % or more of the total reacted productmixture, more preferably 85 wt. % or more, most preferably 90 wt. % ormore.

The process for making the branched ether surfactant compositions of theinvention is flexible in that suitable product can be made under a widerange of operating conditions. The reaction temperature and pressure isnot limited, so long as the reaction proceeds forward within the desiredtime and the product and reactants do not decompose. The reaction iscarried out under conditions effective to react the olefin and diol toproduce the branched primary alcohol composition of the invention.Suitable reaction temperatures range from 50° C. to 250° C., morepreferably from 100° C. to 200° C. The system pressure may besub-atmospheric, atmospheric, or super-atmospheric, depending upon theequipment design and process flow chosen. The residence time in batchoperations ranges from 5 minutes to 3 hours.

In a homogeneous batch process, olefin, diol, and catalyst are added toa reaction vessel and heated. The order of addition is not limited,however, yield of the is increased by adding the diol to the olefin.Accordingly, in a preferred embodiment, olefin and catalyst are heatedin a reaction vessel, and the diol is added to the heated olefin andcatalyst in the reaction vessel.

Sulfation

Anionic surfactants useful in preparing detergents having calciumtolerance and have solubility in cold water include alkyl ether sulfatesof the branched primary alcohol of the invention. These materials havethe respective formulae XOSO₃M, wherein X is represented by the formula

and M is hydrogen or a cation such as ammonium, alkanolammonium(e.g.,triethanolammonium), a monovalent metal cation (e.g., sodium andpotassium), or a polyvalent metal cation (e.g., magnesium and calcium).Preferably, M should be chosen such that the anionic surfactantcomponent is water soluble.

The branched primary alcohol composition may be directly sulfated, orfirst alkoxylated followed by sulfation as described above. Alkoxylationof the branched primary alcohol is described below. The general class ofalcohol alkoxysulfates can be characterized by the chemical formula:

wherein R₁ represents hydrogen or a hydrocarbyl radical having from 1 to3 carbon atoms, R₂ represents a hydrocarbyl radical having from 1 to 7carbon atoms, x is a number ranging from 0 to 16, preferably from 3 to13, A is an alkylene radical, preferably having carbon number in therange of 2 to 4, more preferably 2 or 3, most preferably 2, y is anumber ranging from 1 to 9, wherein the total number of carbon atoms inthe alcohol ranges from 9 to 24, and M is hydrogen or a cation describedabove. AO represent an oxyalkylene group.

The sulfating agents suitable for use in sulfating the branched primaryalcohol or its alkoxylated derivative include those compounds capable offorming the carbon to oxygen to sulfur bonds necessary for the formationof an alkyl ether sulfate or alcohol alkyoxylsulfate. The particularsulfating agents used are typically a function of the compounds to besulfated. These sulfating agents can be any sulfating agent known in theart for the sulfation of alcohols and include sulfur trioxide,chlorosulfonic acid or oleum.

Sulfation processes are described, for instance, in U.S. Pat. No.3,462,525, issued Aug. 19, 1969 to Levinsky et. al., U.S. Pat. No.3,428,654 issued Feb. 18, 1969 to Rubinfeld et. al., U.S. Pat. No.3,420,875 issued Jan. 7, 1969 to DiSalvo et. al., U.S. Pat. No.3,506,580 issued Apr. 14, 1970 to Rubinfeld et. al., U.S. Pat. No.3,579,537 issued May 18, 1971 to Rubinfeld et. al., and U.S. Pat. No.3,524,864 issued Aug. 18, 1970 to Rubinfeld, each incorporated herein byreference. Suitable sulfation procedures include sulfur trioxide (SO₃)sulfation, chlorosulfonic acid (ClSO₃H) sulfation and sulfamic acid(NH₂SO₃H) sulfation. When concentrated sulfuric acid is used to sulfatealcohols, the concentrated sulfuric acid is typically from about 75percent by weight to about 100 percent by weight, preferably from about85 percent by weight to about 98 percent by weight, in water. Suitableamounts of sulfuric acid are generally in the range of from about 0.3mole to about 1.3 moles of sulfuric acid per mole alcohol, preferablyfrom about 0.4 mole to about 1.0 mole of sulfuric acid per mole ofalcohol.

A typical sulfur trioxide sulfation procedure includes contacting thebranched primary alcohol or its alkoxylate and gaseous sulfur trioxideat about atmospheric pressure in the reaction zone of a falling filmsulfator cooled by water at a temperature in the range of from about 25°C. to about 70° C. to yield the sulfuric acid ester of alcohol or itsalkoxylate. The sulfuric acid ester of the alcohol or its alkoxylatethen exits the falling film column and is neutralized with an alkalimetal solution, e.g., sodium or potassium hydroxide, to form the alcoholsulfate salt or the alcohol alkoxylsulfate salt.

The sulfation reaction is suitably carried out at temperatures in therange of from about −20° C. to about 50° C., preferably from about 5° C.to about 40° C., and at pressures in the range of from about 1atmosphere to about 5 atmospheres, preferably from about 1 atmosphere toabout 2 atmospheres, and more preferably, about 1 atmosphere. Suitableresidence times for the sulfation reaction range from a second to anhour, preferably from about 2 minutes to about 30 minutes.

The neutralization reaction is accomplished using one or more bases suchas ammonium or alkali metal or alkaline earth metal hydroxides orcarbonates or bicarbonates dispersed in a non-surfactant carrier.Suitable bases include sodium hydroxide, sodium carbonate, potassiumhydroxide, calcium hydroxide and the like, with ammonium hydroxide,sodium hydroxide or potassium hydroxide being the preferred base. Theamount of base added is in an amount sufficient and in a time sufficientto neutralize the acidity of the alkyl ether sulfonic acid.

The neutralization procedure can be carried out over a wide range oftemperatures and pressures. Typically, the neutralization procedure iscarried out at a temperature in the range of from about 0° C. to about35° C., and typically at atmospheric pressure.

Alkoxylates

Alkoxylates of the branched primary alcohol of the inventions can beprepared by the sequential addition of alkylene oxide to the branchedprimary alcohol in the presence of a catalyst. Any known conventionalalkoxylation method can be used.

The invention is preferably applied to processes utilizing an alkyleneoxide (epoxide) reactant which comprises one or more vicinal alkyleneoxides, particularly the lower alkylene oxides and more particularlythose in the C₂ to C₄ range. In general, the alkylene oxides arerepresented by the formula

wherein each of the R¹, R², R³ and R⁴ moieties is individually selectedfrom the group consisting of hydrogen and alkyl moieties. Reactantswhich comprise ethylene oxide, propylene oxide, or mixtures of ethyleneoxide and propylene oxide are more preferred, particularly those whichconsist essentially of ethylene oxide and propylene oxide. Alkyleneoxide reactants consisting essentially of ethylene oxide are consideredmost preferred from the standpoint of commercial opportunities for thepractice of alkoxylation processes, and also from the standpoint of thepreparation of products having narrow-range ethylene oxide adductdistributions.

An illustration of the branched alkanol alkoxylate product of theinvention by adding y numbers of alkylene oxide molecules to the to thebranched primary alcohol of the invention is presented by the formula:

wherein R₁ represents hydrogen or a hydrocarbyl radical having from 1 to3 carbon atoms, R₂ represents a hydrocarbyl radical having from 1 to 7carbon atoms, x is a number ranging from 0 to 16, preferably from 3 to13, A is an alkylene radical, preferably having carbon number in therange of 2 to 4, more preferably 2 or 3, most preferably 2, y is anumber ranging from 1 to 9, wherein the total number of carbon atoms inthe alcohol ranges from 9 to 24. AO represent an oxyalkylene group.

In terms of processing procedures, the alkoxylation reaction in theinvention may be conducted in a generally conventional manner. Forexample, the catalyst in the liquid active hydrogen containing reactantis contacted, preferably under agitation, with alkylene oxide reactant,which is typically introduced in gaseous form, at least for the loweralkylene oxides.

In preferred embodiments, the alkylene oxide reactant is ethylene oxideor propylene oxide or a mixture of ethylene oxide and propylene oxide.The reaction is carried out in the presence of a catalytically effectiveamount of an alkoxylation catalyst. In a particularly preferredembodiment, ethylene oxide is contacted and reacted with the branchedprimary alcohol of the invention in the presence of a catalyticallyeffective amount of a catalyst for aklkoxylation.

Any conventional alkoxylation catalyst can be used. One example of atypical catalyst is solid or aqueous solution of KOH. Examples of thesecatalyst can be found in U.S. Pat. No. 1,970,578 issued in 1934 and inC. Schoeller and M. Wittmer, German patent no. 605,973 which are hereinincorporated by reference.

Another example of a suitable alkoxylation catalyst is described in U.S.Pat. No. 5,057,627 which is hereby incorporated by reference.Alkoxylation can be catalyzed by phosphate salts of the rare earthelements. These catalysts were typically prepared by adding an aqueoussolution of a rare earth compound such as lanthanum chloride to anaqueous sodium orthophosphate or H₃PO₄ solution.

While these procedures describe a batch mode of operation, the inventionis equally applicable to a continuous process.

Overall, the two reactants are utilized in quantities which arepredetermined to yield an alkoxylate product of the desired mean oraverage adduct number. The average adduct number of the product is notcritical to this process. Such products commonly have an average adductnumber in the range from less than one to about 30 or greater.

In general terms, suitable and preferred process temperatures andpressures for purposes of this invention are the same as in conventionalalkoxylation reaction between the same reactants, employing conventionalcatalysts. A temperature of at least about 90° C., particularly at leastabout 120° C., and most particularly at least about 130° C., istypically preferred from the standpoint of the rate of reaction, while atemperature less than about 250° C., particularly less than about 210°C., and most particularly less than about 190° C., is typicallydesirable to minimize degradation of the product. As is known in theart, the process temperature can be optimized for given reactants,taking such factors into account.

Superatmospheric pressures, e.g., pressures between about 10 and 150psig, are preferred, with pressure being sufficient to maintain theactive hydrogen containing reactant substantially in the liquid state.

When the alkylene oxide reactant is a vapor, alkoxylation is thensuitably conducted by introducing alkylene oxide into a pressure reactorcontaining the alcohol reactant and the catalyst. For considerations ofprocess safety, the partial pressure of a lower alkylene oxide reactantis preferably limited, for instance, to less than about 60 psia, and/orthe reactant is preferably diluted with an inert gas such as nitrogen,for instance, to a vapor phase concentration of about 50 percent orless. The reaction can, however, be safely accomplished at greateralkylene oxide concentration, greater total pressure and greater partialpressure of alkylene oxide is suitable precautions, known to the art,are taken to manage the risks of explosion. A total pressure of betweenabout 40 and 110 psig, with an alkylene oxide partial pressure betweenabout 15 and 60 psig, is particularly preferred, while a total pressureof between about 50 and 90 psig, with an alkylene oxide partial pressurebetween about 20 and 50 psig, is considered more preferred.

The time required to complete a process according to the invention isdependent both upon the degree of alkoxylation that is desired (i.e.,upon the average alkylene oxide adduct number of the product) as well asupon the rate of the alkoxylation reaction (which is, in turn dependentupon temperature, catalyst quantity and nature of the reactants). Atypical reaction time for preferred embodiments, particularly for whenthe alkylene oxide is gaseous is less than 24 hours.

After the alkoxylation reaction has been completed, the product ispreferably cooled. If desired, catalyst can be removed from the finalproduct, although catalyst removal is not necessary to the process ofthe invention. Catalyst residues may be removed, for example, byfiltration, precipitation, extraction, or the like. A number of specificchemical and physical treatment methods have been found to facilitateremoval of catalyst residues from a liquid product. Such treatmentsinclude contact of the alkoxylation product with strong acids such asphosphoric and/or oxalic acids or with solid organic acids such asNAFION H+ or AMBERLITE IR 120H; contact with alkali metal carbonates andbicarbonates; contact with zeolites such as type Y zeolite or mordenite;or contact with certain clays. Typically, such treatments are followedby filtration or precipitation of the solids from the product. In manycases filtration, precipitation, centrifugation, or the like, is mostefficient at elevated temperature.

The tolerance of the sulfated branched primary alcohols to calcium ionswas determined by titration of test solutions of each of the compoundswith calcium chloride. Specifically, the tolerance of the anionicsurfactants to calcium ions was determined by taking ten (10) cc's of a0.06% by weight anionic surfactant solution in distilled water adjustedto a pH of 5 using sodium hydroxide, added to a capped bottle, andplaced into a oven maintained at 40° C. Addition of 10 micro literaliquots of 10% solutions of calcium chloride in distilled water addedto provoke a precipitate formation from the reaction of the surfactantand the salt. After a sufficient amount of time had elapsed forequilibration and phase separation, the clear, top, portion was measuredfor activity by/via the two phase titration method disclosed in Reid, V.W.,G. F. Longman and E. Heinerth, “Determination of Anionic-ActiveDetergents by Two-phase Titration,” Tenside 4, 1967, 292-304. Thereported calcium chloride tolerance is the ppm amount of calciumchloride which was added to precipitate fifty (50) weight % of theanionic surfactant.

The sulfated branched primary alcohol compositions of the invention haveseveral orders of magnitude higher calcium tolerance over linearalkylbenzene sulfonates and branched alkyl sulfates having the samecarbon number. In one embodiment, there is provided a sulfated branchedprimary alcohol composition and derivatives thereof having a calciumtolerance of 5000 ppm CaCl₂ or more. Preferably, the sulfated branchedprimary alcohol primary composition and derivatives thereof having acalcium tolerance of 20,000 CaCl₂ or more, more preferably 50,000 ppm ormore, most preferably 75,000 or more, and even 100,000 ppm or more. Bycomparison, linear alkylbenzene sulfonates have calcium tolerance valuesunder 250, linear alkylsulfates have calcium tolerance values under 100,and branched alkyl sulfates have calcium tolerance values under 500.

Such high calcium tolerance renders the surfactant compositions made bythe branched, primary alcohol compositions of the invention suitable foruse in aqueous media having large levels of electrolytes. In oneembodiment, there is provided a surfactant composition which is tolerantto aqueous media containing at least 100,000 ppm calcium chloride.

In another embodiment, there is provided a surfactant composition whichis tolerant to sea water having a salinity of at least 25,000 ppm,preferably at least 30,000, more preferably about 34,000 ppm or more oftotal dissolved solids, and a cumulative amount of calcium and magnesiumof at least 1000 ppm, more preferably at least 1500 ppm, most preferablyat least 1700 ppm.

A useful test to determine whether a surfactant solution is tolerant tosea water is as follows: a 0.06% active surfactant solution in sea wateris prepared and visually inspected for turbidity. The composition shownbelow, was visually observing whether any surfactant precipitates (fail)or whether no precipitation occurs (pass).

The sea water used for a test to determine whether a particularsurfactant composition is tolerant to sea water has a composition ofabout 34 ppt salinity, with an ion concentration as follows:

ION Conc. (mg/l) ION Conc. (mg/l) Chloride 19251 Sodium 10757 Sulfate2659 Magnesium 1317 Potassium 402 Calcium 398 Carbonate/Bicarbonate 192Strontium 8.6 Boron 5.6 Bromide 2.3 Iodide 0.22 Lithium 0.18Trace amounts of between 0.01 and 0.05 mg/l of each of copper, iron,nickel, zinc, maganese, molybdenum, cobalt, vanadium, aluminum, bariumand fluorine are present. Other trace amounts of elements are be presentin the following quantities:

-   Lead at <0.005 mg/l-   Arsenic at <0.0002 mg/l-   Chromium at <0.0006 mg/l    Trace amounts of Tin, Antimony, Rubidium and Selenium No or 0    amounts of Mercury, Nitrate and Phosphate.

In an independent embodiment of the invention, the branched ethersurfactant compositions of the invention exhibit low Krafft temperaturepoints. The Krafft temperature of anionic surfactants are measured bydiluting the anionic surfactant to a homogeneous aqueous 1 weight %surfactant solution in water, freezing 25 cc aliquots of the solution ina freezer overnight at approximately −4 deg C. to force the surfactantout of solution, and then warming the solution in atemperature-controlled water bath in one degree intervals at a rate ofone degree/hour. The reported Krafft temperature is the lowesttemperature where the solution is fully transparent as determined byvisual inspection.

In this embodiment, the sulfates of the branched ether primary alcohols,their derivatives, and their branched ether surfactant compositionsexhibit Krafft temperatures of 10° C. or less, more preferably 0° C. orless. The branched ether surfactant compositions containing the sulfatesof the branched ether primary alcohols and/or their derivatives arehighly soluble in the aqueous wash media, thereby contributing toimproved detergency performance and reducing the tendency towardprecipitation, especially at colder wash temperatures of 50° F. (10° C.)or less.

In yet another independent embodiment of the invention, the branchedether surfactant compositions of the invention exhibit cold waterdetergency values of at least 22% measured at 50° F. (10° C.). In apreferred embodiment, the branched ether surfactant composition has acold water detergency value of at least 28% measured at 50° F. In yet amore preferred embodiment, the sulfates of the branched ether primaryalcohols, their derivatives, and their branched ether surfactantcompositions simultaneously exhibit cold water detergency values of atleast 22% at 50° F. (10° C.), Krafft temperatures of 10° C. or less,more preferably 0° C. or less, and has a calcium tolerance of 5000 ppmCaCl₂ or more.

The detergency evaluations can be conducted from a standard high densitylaundry powder (HDLP) Detergency/Soil Redeposition Performance test. Theevaluations can be conducted using Shell Chemical Company's radiotracertechniques at 50° F. and 90° F. temperatures at a water hardness of 150ppm as CaCO₃ (CaCl₂/MgCl₂=3/2 on a molar basis). The sulfated branchedether surfactant compositions of the invention can be tested, on a ¼ cupbasis, against multisebum, cetanesqualane and clay soiled permanentpress 65/35 polyester/cotton (PPPE/C) fabric. The HDLP's is tested at0.74 g/l concentration, containing 27 wt % of the sulfated branchedether surfactant composition, 46 wt % of builder (zeolite-4A), and 27 wt% of sodium carbonate.

The composition of the radiolabeled Multisebum Soil is as follows:

Component Label % wt. Cetane  3H 12.5 Squalane  3H 12.5 Trisearin  3H 10Arachis (Peanut)  3H 20 Oil Cholesterol 14C  7 Octadecanol 14C  8.0Oleic Acid 14C 15.0 Stearic Acid 14C 15.0

A Terg-O-Tometer is used to wash the swatches at 15 minutes intervals.The wash conditions are set to measure both cold water detergency at 50°F. and warm water detergency at 90° F. The agitation speed is 100 rpm.Once the 4″×4″ radiotracer soiled swatches are washed by theTerg-O-Tometer, they are hand rinsed. The wash and rinse waters arecombined for counting to measure sebum soil removal. The swatches arecounted to measure clay removal.

For details concerning the detergency methods and radiotracertechniques, reference may be had to B. E. Gordon, H. Roddewig and W. T.Shebs, HAOCS, 44:289 (1967), W. T. Shebs and B. E. Gordon, JAOCS, 45:377(1968), and W. T. Shebs, Radioisotope Techniques in Detergency, Chapter3, Marcel Dekker, New York (1987), each incorporated herein byreference.

The sulfates of the branched ether surfactant compositions of theinvention are also biodegradable. The biodegradation testing methods formeasuring the biodegradability of the sulfates can be conducted inaccordance with the test methods established in 40 CFR §796.3200, alsoknown as the OECD 301D test method, incorporated herein by reference. Bya biodegradable composition or surfactant is meant that that thecompound or composition gives a measured biochemical oxygen demand (BOD)of 60% or more within 28 days, and this level must be reached within 10days of biodegradation exceeding 10 percent.

The Krafft point can be measured by preparing 650 ml of a 0.1%dispersion of glycasuccinimide in water by weight. If the surfactant wassoluble at room temperature, the solution was slowly cooled to 0° C. Ifthe surfactant did not precipitate out of solution, its Krafft point wasconsidered to be <0° C. (less than zero). If the surfactant precipitatedout of solution, the temperature at which precipitation occurs was takenas the Krafft point.

If the surfactant was insoluble at room temperature, the dispersion wasslowly heated until the solution became homogeneous. It was then slowlycooled until precipitation occurred. The temperature at which thesurfactant precipitates out of solution upon cooling was taken as theKrafft point.

Detergent Compositions

The sulfated branched primary alcohol or alcohol alkoxylsulfatecomposition of the invention find particular use in detergents,specifically laundry detergents. The alkoxylated branched primaryalcohol composition of the invention also find particular use indetergents, specifically dishwashing detergents. Particularly, thesealkoxylated branched primary alcohol composition of the invention havelow odor compared with conventional detergent range alkoxylated alcoholcomposition currently available commercially. A biodegradable detergentcomposition can be prepared using the branched ether derivativecompositions of the invention.

The detergent compositions are generally comprised of a number ofcomponents, besides the sulfated primary alcohol, alcoholalkoxylsulfate, or alkoxylated branched primary alcohol composition ofthe invention. The detergent composition may include: other surfactantsof the ionic, nonionic, amphoteric or cationic type; builders(phosphates, zeolites), and optionally cobuilders (polycarboxylates);bleaching agents and their activators; foam controlling agents; enzymes;anti-greying agents; optical brighteners; and stabilizers.

Such additional detergent components useful for the invention aredescribed in detail U.S. Pat. Nos. 6,087,311; 6,083,893; 6,159,920;6,153,574; WO-A-9405761; and GB1429143. The disclosures are herebyincorporated by reference.

The following Examples are provided to further illustrate certainspecific aspects of the invention but are not intended to limit itsbroader scope.

EXAMPLE 1

A reaction of 1-dodecene with 1,3-propanediol using a homogeneous acidcatalyst, p-toluene sulfonic acid, to manufacture the surfactant of theinvention is provided.

To a 500 ml round bottom flask equipped with an overhead stirrer,condenser and N₂ inlet system was added 100 grams (0.6 moles) of1-dodecene (acquired from Aldrich Chemical Company) and 137 grams (1.8moles) of 1,3-propanediol (obtained from Shell Chemical Company) and4.56 grams (0.024 moles) of toluene sulfonic acid monohydrate. Themixture was heated to 150° C. for four hours at which time the reactionmixture was cooled to room temperature.

The reaction mixture consisted of two phases at room temperature. Thetwo phases were separated by a separatory funnel. Each phase wasanalyzed by gas chromatography. 130 g of liquid were recovered in thetop phase, and 107 g of liquid were recovered in the bottom phase.Analysis of the top phase indicated the formation of 24% wt of3-dodecyloxy-1-propanol product, 72% wt unreacted dodecenes, 2% wtdodecene dimers and 2% wt 1,3-propanediol, didocecyl ether, based on theweight of the top phase liquid. There was less than 1% wt1,3-propanediol or 1,3-propane diol oligomers in the top phase,indicating good phase separation. Analysis of the bottom phase indicated94% wt unreacted 1,3-propanediol with about 6 wt % linear dimer of thepropanediol, based on the weight of the bottom phase liquid. There wasless than 1% wt dodecene or other dodecyl based adducts in the bottomphase, further confirming good phase separation between the product andunreacted olefin in the upper phase and the propane diol and dimersthereof in the lower phase.

Removal of the unreacted dodecenes in the upper phase by distillationafforded 29.5 grams of a mixture of isomers of3-dodecyleneoxy-1-propanol. Selectivity to the 3-dodecyloxy-1-propanolproduct was 97%.

EXAMPLE 2

The reaction in example 1 was repeated using a lower quantity of1,3-propanediol, and by adding the 1,3-propanediol to the 1-dodeceneslowly during the reaction. To a 500 ml round bottom flask equipped withan overhead stirrer, condenser and N₂ inlet system was added 168 grams(1.0 mole) of 1-dodecene (acquired from Aldrich Chemical Company) and2.25 grams(0.01 moles) of toluene sulfonic acid monohydrate. The mixturewas heated to 150 C. at which time 23 grams (0.3 moles) of1,3-propanediol (obtained from Shell Chemical Company) was added slowlyat the rate of 10 grams per hour. The reaction was stirred for anadditional hour after the 1,3-propanediol had been added. The reactionmixture was cooled to room temperature.

The reaction mixture consisted of two discrete phases at roomtemperature. Dodecene was removed from the upper phase via distillationaffording 15 grams of a clear oil. Analysis of this product mixture bygas chromatography indicated the formation of 74% wt3-dodecyloxy-1-propanol, 24% wt of 1,3-propanediol, didodecyl ether and2% wt dodecene dimer. Analysis of the bottom layer showed 98% wtunreacted 1,3-propanediol and 2% wt linear dimer of 1,3-propanediol(3-hydroxypropyleneoxy-1-propanol).

EXAMPLE 3

Addition of 1,3-propanediol to 1-dodecene is provided using anotherhomogeneous catalyst, trifluoromethanesulfonic acid, as catalyst.

The reaction in example 2 was repeated using 1 gram (0.0067 moles) oftrifluoromethanesulfonic acid as catalyst instead of p-toluenesulfonicacid. The reaction mixture was cooled to room temperature. The reactionmixture consisted of two phases. Dodecene was removed from the upperphase via distillation affording 23 grams of a clear oil. Analysis ofthis product mixture by gas chromatography indicated the formation of69% w 3-dodecyloxy-1-propanol, 22% w of 1,3-propanediol, didodecyl etherand 9% w dodecene dimer. Analysis of the bottom layer showed 93% wunreacted 1,3-propanediol and 7% w linear dimer of 1,3-propanediol(3-hydroxypropyleneoxy-1-propanol).

EXAMPLE 4

Reaction of 1-dodecene with 1,3-propanediol is provided using aheterogeneous catalyst, beta H⁺ zeolite as catalyst.

To a 500 ml round bottom flask equipped with an overhead stirrer,condenser and N2 inlet system was added 100 grams (0.6 moles) of1-dodecene (acquired from Aldrich Chemical Company) and 137 grams (1.8moles) of 1,3-propanediol (obtained from Shell Chemical Company) and 10grams of beta zeolite powder, H⁺ form (obtained from ZeolystCorporation). The mixture was heated to 150° C. for two hours at whichtime the reaction mixture was cooled to room temperature.

The reaction mixture consisted of two phases, with the powdered zeolitecatalyst suspended in the bottom phase. The reaction mixture was dilutedwith 250 ml of heptane and 250 ml of distilled water, mixed well and thetwo phases separated using a separatory funnel. The top phase wasisolated, and the heptane was removed by rotary evaporation affording23.2 grams of clear oil.

Analysis of this product indicated the formation of 94% wt3-dodecyloxy-1-propanol, 4% wt 3-dodecyoxypropyloxy-1-propanol and 2% wdodecene dimers. C¹³ NMR analysis indicated that the3-dodecyloxy-1-propanol was a mixture of isomers with 95% wt of thehydroxypropyl group attached at the 2-carbon position (relative to thealpha carbon atoms) of the dodecyl moiety to produce a methyl branchedproduct (I₁) and 5% wt of the hydroxypropyl group attached at the3-carbon position to produce an ethyl branched product (I₂). There was<1% w of attachment at the 4 (I₃) and the higher carbon positions. Theisomers have the following structural formulas, respectively:

EXAMPLE 5

Reaction of NEODENE 14 Olefin (NEODENE is a trademark of Shell group ofcompanies) with 1,3-propanediol using beta H+zeolite as catalyst isprovided.

The reaction of Example 4 was repeated except that 118 grams (0.6 moles)of NEODENE 14 Olefin (1-tetradecene obtained from Shell ChemicalCompany) was used in place of 1-dodecene as the olefin. After thereaction mixture was cooled to room temperature, there resulted twodiscrete phases, each of which were analyzed by gas chromatography. Theupper phase indicated the formation of 70% w unreacted tetradecenes, 27%w of isomers of 3-tetradecyloxy-1-propanol, ˜3% w of the3-tetradecyloxypropyloxy-1-propanol. Analysis of the bottom phase showed94% w unreacted 1,3-propanediol, 5% w hydroxypropyloxy-1-propanol and atrace of higher trimer of 1,3-propanediol (i.e. oligomer).

EXAMPLE 6

Reaction of NEODENE 16 Olefin with 1,3-propanediol using beta Zeolite asCatalyst is provided.

The reaction of Example 4 was repeated except that 135 grams (0.6 moles)of 16 Olefin (1-hexadecene obtained from Shell Chemical Company) wasused in place of 1-dodecene as the olefin. After the reaction mixturewas cooled to room temperature, both phases from the product mixturewere analyzed by gas chromatography. The upper phase indicated theformation of 72% w hexadecenes, 25% w of isomers of3-hexadecyloxy-1-propanol, ˜3% w of the3-hexadecyloxypropyloxy-1-propanol. Analysis of the bottom phase showed96% w unreacted 1,3-propanediol, 4% w hydroxypropyloxy-1-propanol and atrace of higher trimer of 1,3-propanediol (i.e. oligomer).

EXAMPLE 7

Reaction of NEODENE 12 Olefin with 1,3-propanediol using anotherheterogeneous catalyst, CBV-500 Zeolite, as the catalyst is provided.

The reaction of Example 4 was repeated except that 100 grams (0.6 moles)of NEODENE® 12 Olefin (1-dodecene obtained from Shell Chemical Company)was used in place of 1-dodecene as the olefin and 10 grams of CBV-500zeolite as catalyst. CBV-500 zeolite is a Y-type zeolite obtained fromZeolyst International. After about 3.5 hours of reaction time, thereaction mixture was cooled to room temperature, and both phases fromthe product mixture were analyzed by gas chromatography. The upper phaseindicated the formation of 90% w unreacted dodecenes, 9% w of isomers of3-dodecyloxy-1-propanol product, and trace amounts of the3-dodecyloxypropyloxy-1-propanol. Analysis of the bottom phase showed98% w unreacted 1,3-propanediol and 2% w 3-hydroxypropyloxy-1-propanol.

EXAMPLE 8

A reaction of NEODENE 12 Olefin with 1,3-propanediol using anotherheterogeneous catalyst, CBV-780 Zeolite as Catalyst is provided.

The reaction of Example 4 was repeated except that 100 grams (0.6 moles)of NEODENE 12 Olefin (1-dodecene obtained from Shell Chemical Company)was used in place of 1-dodecene as the olefin and 10 grams of CBV-780Zeolite as catalyst. This catalyst is a modified Y-type zeolite obtainedZeolyst International. After the reaction mixture was cooled to roomtemperature, both phases from the product mixture were analyzed by gaschromatography. The upper phase indicated the formation of 90% wdodecenes, 9% w of isomers of 3-dodecyloxy-1-propanol product, and traceamounts of the 3-dodecyloxypropyloxy-1-propanol. Analysis of the bottomphase showed 98% w unreacted 1,3-propanediol and 2% w3-hydroxypropyloxy-1-propanol.

EXAMPLE 9

A reaction of NEODENE 12 Olefin with 1,3-propanediol using anotherheterogeneous catalyst, CBV-740 Zeolite as Catalyst is provided.

The reaction of Example 4 was repeated except that 100 grams (0.6 moles)of NEODENE 12 Olefin (1-dodecene obtained from Shell Chemical Company)was used in place of 1-dodecene as the olefin and 10 grams of CBV-740Zeolite as catalyst. CBV-740 zeolite is a modified Y-zeolite obtainedfrom Zeolyst International. After the reaction mixture was cooled toroom temperature, both phases from the product mixture were analyzed bygas chromatography. The upper phase indicated the formation of 91% wdodecenes, 8% w of isomers of 3-dodecyloxy-1-propanol product, and traceamounts of the 3-dodecyloxypropyloxy-1-propanol. Analysis of the bottomphase showed 98% w unreacted 1,3-propanediol and 2% w3-hydroxypropyloxy-1-propanol.

EXAMPLE 10

A reaction of NEODENE 12 Olefin with 1,3-propanediol using anotherheterogeneous catalyst, 13× Molecular Sieve as Catalyst is provided.

The reaction of Example 4 was repeated except that 100 grams (0.6 moles)of NEODENE 12 Olefin (1-dodecene obtained from Shell Chemical Company)was used in place of 1-dodecene as the olefin and 10 grams of 13×Molecular Sieve obtained from PQ Corporation as catalyst. After thereaction mixture was cooled to room temperature, both phases from theproduct mixture were analyzed by gas chromatography. The upper phaseindicated the formation of 82% w dodecenes, 16% w of isomers of3-dodecyloxy-1-propanol product, and 2% w of the3-dodecyloxypropyloxy-1-propanol. Analysis of the bottom phase showed96% w unreacted 1,3-propanediol and 4% w 3-hydroxypropyloxy-1-propanol.

EXAMPLE 11

A reaction of NEODENE 12 Olefin with 1,3-propanediol using anotherheterogeneous catalyst, a H⁺ Y Zeolite as Catalyst is provided.

The reaction of Example 4 was repeated except that 100 grams (0.6 moles)of NEODENE® 12 Olefin (1-dodecene obtained from Shell Chemical Company)was used in place of 1-dodecene as the olefin and 10 grams of H⁺ YZeolite prepared by treatment of a Na—Y Zeolite(CBV-100 obtained fromZeolyst International) with ammonium nitrate followed by calcination at500° C. in air for 8 hours was used as the catalyst. After the reactionmixture was cooled to room temperature, both phases from the productmixture were analyzed by gas chromatography. The upper phase indicatedthe formation of 94% w dodecenes and 6% w of isomers of3-dodecyloxy-1-propanol product. No appreciable3-dodecyloxypropyloxy-1-propanol was observed. Analysis of the bottomphase showed 96% w unreacted 1,3-propanediol and 4% w3-hydroxypropyloxy-1-propanol.

EXAMPLE 12

A reaction of C15/C16 internal olefins with 1,3-propanediol (PDO) usinga homogeneous catalyst, p-toluenesulfonic acid, is provided.

To a 500 ml Zipperclave autoclave was added 44 grams (0.2 moles) of amixture of C15/C16 internal olefins obtained from Shell ChemicalCompany, 76 grams (1 mole) of 1,3-propanediol (acquired from ShellChemical Company) and 0.38 grams (0.002 moles) of p-toluene sulfonicacid in 100 ml of tetrahydrofuran. The autoclave system was placed underN2 atmosphere after removal of air by repeated pressurization anddepressurization with N₂. Then the pressure of the Zipperclave wasadjusted to 50 psig N₂. The reaction was heated to 100° C. for 18 hours.The reaction was cooled to 25° C. The tetrahydrofuran solvent wasremoved by rotary evaporation producing two phases. The two phases wereseparated by separatory funnel.

Each phase was analyzed by gas chromatography. The upper phase indicatedthe formation of about 6% wt of the 1,3-propanediol adduct of themixture of C15/C16 olefins. The balance was isomerized C15/C16 olefins.The lower phase consisted of 98% wt 1,3-propanediol and 2% wt3-hydroxypropyl-1-propanol.

EXAMPLE 13

A reaction of C15/C16 internal olefins with PDO using p-toluenesulfonicacid as catalyst.

Example 12 was repeated except that 88 grams (0.4 moles) of a mixture ofan internal C15/C16 olefin mixture obtained from Shell Chemical Companyand 100 ml of dimethoxyethane was used as solvent. After the reactionwas cooled to 25 C. the dimethoxyethane solvent was removed by rotaryevaporation producing two phases. The phases were separated byseparatory funnel. Each phase was analyzed by gas chromatography. Theupper phase indicated the formation of 8% w of the 1,3-propanedioladduct of the mixture of C15/C16 olefins. The balance was isomerizedC15/C16 olefins. The lower phase consisted of 98% w 1,3-propanedioll and2% w 3-hydroxypropyl-1-propanol.

EXAMPLE 14

A reaction of isomerized C15/C16 Olefins obtained from Shell ChemicalCompany with PDO using a homogeneous catalyst, trifluoromethane sulfonicacid is provided.

Example 13 was repeated except 0.3 grams (0.002 moles) oftrifluoromethanesulfonic acid was used as catalyst. After the reactionwas cooled to 25 C. The dimethoxyethane solvent was removed by rotaryevaporation producing two phases. Each phase was analyzed by gaschromatography. The upper phase indicated the formation of ˜15% w of the1,3-propanediol adduct of the mixture of C15/C16 olefins and 2% w of thehydroxypropoxypropyloxy adduct of the mixture of C15/C16 olefins. Thebalance was isomerized C15/C16 olefins. The lower phase consisted of 98%w 1,3-propanediol and 2% w 3-hydroxypropyl-1-propanol.

EXAMPLE 15

A reaction of 1-Dodecene with 1,3-propanediol using p-toluenesulfonicacid as catalyst and dimethoxyethane as solvent is provided.

To a 500 ml Zipperclave autoclave was added 67.2 grams (0.4 moles) of1-dodecene [acquired from Aldrich Chemical Company], 76 grams (1 mole)of 1,3-propanediol [acquired from Shell Chemical Company] and 0.38 grams(0.002 moles) of p-toluene sulfonic acid in 100 ml of dimethoxyethane.The autoclave system was placed under N₂ atmosphere after removal of airby repeated pressurization and depressurization with N₂. Then thepressure of the Zipperclave was adjusted to 50 psig N₂. The reaction washeated to 150° C. for 3 hours. The reaction was cooled to 25° C. Thedimethoxyethane solvent was removed by rotary evaporation producing twophases. Each phase was analyzed by gas chromatography. The upper phaseindicated the formation of ˜11% w of 3-dodecyloxy-1-propanol and 89% wmixed dodecenes. The lower phase consisted of 97% w 1,3-propanediol and3% w 3-hydroxypropyl-1-propanol.

EXAMPLE 16

A Reaction of 1-Dodecene with 1,3-propanediol usingtrifluoromethanesulfonic acid as catalyst and dimethoxyethane solvent isprovided.

Example 14 was repeated using 0.3 grams (0.002 moles) oftrifluoromethanesulfonic acid as catalyst. The reaction was cooled to 25C. The dimethoxyethane solvent was removed by rotary evaporationproducing two phases. The dodecene was removed from the upper phase bydistillation affording 2.3 grams of clear oil. Analysis indicated thisproduct to be 3-dodecyloxy-1-propanol.

EXAMPLE 17

A reaction of 1-Dodecene with 1,3-propanediol usingtrifluoromethanesulfonic acid as catalyst without a solvent is provided.

Example 14 was repeated using 0.3 grams (0.002 moles) oftrifluoromethanesulfonic acid as catalyst but no solvent. The reactionwas cooled to 25 C. producing two phases. The dodecene was removed fromthe upper phase by distillation affording 9.4 grams of clear oil.Analysis indicated this product to be 3-dodecyloxy-1-propanol.

EXAMPLE 18

A Reaction of NEODENE 12 Olefin with PDO using a heterogeneous catalyst,CBV-500 Zeolite as catalyst is provided.

To a 500 ml round bottom flask equipped with an overhead stirrer,condenser and N₂ inlet system was added 100 grams (0.6 moles) of NEODENE12 Olefin (obtained from Shell Chemical Company) and 137 grams (1.8moles) of 1,3-propanediol (obtained from Shell Chemical Company) and 10grams of CBV-500 Zeolite, a Y zeolite obtained from ZeolystInternational. The mixture was heated to 150° C. for two hours at whichtime the reaction mixture was cooled to room temperature. The reactionmixture consisted to two phases and each phase was analyzed by gaschromatography. Analysis of the top phase indicated the formation of 4%w of 3-dodecyloxy-1-propanol and 96% w mixed dodecenes. Analysis of thebottom phase indicated 99% wt unreacted 1,3-propanediol with 1% wtlinear dimer.

EXAMPLE 19

A reaction of NEODENE 12 Olefin with PDO using another heterogeneouscatalyst, CBV-712 Zeolite is provided.

Example 18 was repeated using 10 grams of CBV-712 Zeolite as catalyst.CBV-712 zeolite is a modified Y-zeolite obtained from ZeolystInternational. Analysis of the top phase indicated the formation of 3% wof 3-dodecyloxy-1-propanol and 97% w mixed dodecenes. Analysis of thebottom phase indicated 99% wt unreacted 1,3-propanediol with ˜1% wtlinear dimer

EXAMPLE 20

Experiments were conducted using a fixed bed reactor system consistingof a 20 mm×220 mm 316 stainless steel tubular reactor which was fittedwith a thermowell transversing the center of the tube and containingthree temperature control/indicator thermocouples at the top, middle andbottom of the reactor. The tube was filled with 20 ml of CP861E betazeolite extrudate obtained from Zeolyst International which had beencalcined at 500° C. for 6 hours. The catalyst system was purged with N₂.NEODENE 12 Olefin and 1,3-propanediol were pumped separately to thereactor system at 20 ml/hr each initially at 25° C. and 1 atmosphere ofN₂. The reactor system was heated to 150° C. and pumping continued for 8hours. The product mixture separated into two clear, colorless phases at25° C. and was analyzed by gas chromatography. Analysis of the upperphase showed the formation of 21% w 3-(2-methylundecyloxy)-1-propanol,4% w 3-(2-ethyldecyloxy)-1-propanol and ˜1% dodecene dimers. Theremainder was a mixture of dodecenes. The lower phase contained 94% wunreacted 1,3-propanediol and 6% w linear dimer of PDO.

EXAMPLE 21

A larger scale reaction of NEODENE 12 Olefin with PDO Using beta H+Zeolite Catalyst is provided.

A total of 2352 grams (14 moles) of NEODENE 12 Olefin obtained fromShell Chemical Company, 3192 grams (42 moles) of 1,3-propanediol and 200grams of beta H+ Zeolite obtained from Zeolyst International were addedto a 12 liter resin vessel fitted with overhead stirrer, thermowell,condenser and N₂ gas inlet/outlet system. The mixture was mixed well andheated to 150° C. for 5 hours. The reaction mixture was cooled to 25°C., resulting in the formation of two phases. The two phases wereseparated by separatory funnel. Each phase was analyzed by gaschromatography. Analysis of the top phase indicated the formation of25.2% w of the 1-PDO adduct of NEODENE 12 Olefin, 2.0% w of the lineardi-PDO adduct of NEODENE 12 Olefin, 4.4% w dodecene dimers and 68.4% wisomerized dodecenes. Analysis of the bottom phase indicated 90% wunreacted 1,3-propanediol, and 10% w linear di-PDO dimer. Distillationof the dodecenes from the upper phase afforded 858 grams of a clear,fluid liquid. Analysis of this material by C¹³ NMR indicated theformation of 94% of the 1-PDO adduct of NEODENE 12 Olefin (of which 95%w was 3-(2-methylundecyloxy)-1-propanol and 5% w was3-(3-ethyldecyloxy)-1-propanol) and 6% w was the linear PDO dimer (orPDO-2) adduct of NEODENE 12 Olefin.

EXAMPLES A-C

Examples of sulfated products derived from C₁₂, C₁₄, and C₁₆ branchedprimary alcohols, prepared in a manner similar to Example 6,respectively Examples A, B, and C, were produced according to thefollowing method.

0.666 moles of the respective branched primary alcohol were dissolved in300 mls of methylene chloride in a 500 ml multineck round bottom flaskequipped with an addition funnel and stirring bar. The reaction mixturewas cool to 0° C. 0.7 moles of chlorosulfonic acid was transferred tothe addition funnel and added dropwise over a 15 minute period. Theproduct was neutralized by pouring the reaction mixture into a wellstirred aqueous solution of 0.7 moles of sodium hydroxide dissolved inapproximately 800 mls of distilled water. The methylene chloride wasremoved from the mixture by reduced pressure. This produced anapproximately 25 weight percent active solution of the desired sulfatedproducts of the branched primary alcohols. The products were all clearfluid pale yellow liquids. Example A is C₁₂-1 PDOS. Example B is C₁₄-1PDOS. Example C is C₁₆-1 PDOS.

For comparison, the properties of a primary alcohol sulfate produced bysulfation of NEODOL 23 Alcohol (mixture of C₁₂ and C₁₃ having typicalhydroxyl number of 289 mg/gKOH) in a similar manner to those aboveobtained from Shell Chemical Co. and Witconate 1260, a 60% aqueoussolution of C₁₂ linear alkyl sulfate (C₁₂ LAS) from Witco Corp. areprovided.

RELATIVE STRENGTHS Physical Property C₁₂ C₁₂ −1 C₁₄ −1 C₁₆ −1 AttributesLAS N23-S PDOS PDOS PDOS Solubility ° C. (+) (−) (+) (+) (−) CriticalMicelle (−) (−) (+) (+) (++) Conc. (CMC) @ 25° C. Hardness Tolerance (−)(−) (+++) (++) (+) Ca ⁺⁺ Interfacial Tension (++) (++) (−) (−) (+) 4/1Cetane/oleic acid Interfacial (+) (+) (−) (−) (+) Tension HexadecaneOther IFT in (−) None (+) (+) (+) Seawater 4/1 above Solubility in (−)(−) (+) (+) (−) Seawater

ACTUAL VALUES Physical Property C₁₂ C₁₂ −1 C₁₄ −1 C₁₆ −1 Attributes LASN23-S PDOS PDOS PDOS Solubility ° C. 0 29 0 0 22 Krafft 1.0% SolutionCritical Micelle 0.070 0.140 0.062 0.029 0.0063 Conc. (CMC) @ Wt % Wt %Wt % Wt % Wt % 25° C. Surface Tension 34 25 28 30 33 (Dynes/Cm.) @ CMCFoam Rate (cc/min) 110 100 100 133 102 Foaming Stability * 14 20 10 1416 Hardness Tolerance 140 18 >120,000 30,200 1,800 Ca ⁺⁺ ppm ppm ppm ppmppm Interfacial Tension 0.5 0.5 5.3 2.5 1.4 4/1 Cetane/oleic acidInterfacial 6.4 5.7 13.6 9.3 6.3 Tension Hexadecane I Other IFT in 0.5None 0.12 0.11 0.17 Seawater 4/1 above Solubility in Cloudy Cloudy ClearClear Cloudy Seawater {overscore (ω)} Ppt. Ppt. Ppt. * Centimeter offoam remaining after 20 minutes in DI water @ 25° C. and 0 ppm hardness.I Average Dynes/Centimeter in 0.1% solution at 25° C. over more than onehour. {overscore (ω)} Seawater is 3.589% synthetic salt that containsevery major, minor and trace element found in original seawater. Partsper million concentration, ppm, is 35,890 ppm.

EXAMPLES D-F

Examples of ethoxylated products derived from C₁₂, C₁₄, and C₁₆ branchedprimary alcohols, prepared in a manner similar to Example 6,respectively Examples D, E, and F, were produced according to thefollowing method.

7 moles of Ethylene oxide was introduced into a pressure reactorcontaining 1 mole the respective branched primary alcohol reactant andKOH as catalyst at a partial pressure of 30 psig and diluted withNitrogen gas to a total pressure of 60 psig. The reaction was carriedout at a temperature of 160° C. for a period of 2 hours. The ethyleneoxide-alcohol adduct produced had an average 7 EO repeating units.

For comparison, the properties of an alcohol ethoxylate having anaverage of 7 ethoxylate repeat units prepared by ethoxylation of NEODOL25 alcohol obtained from Shell Chemical Co. is provided.

Cloud point and phase behavior was measured as follows: A temperaturescan is normally completed on a 1% solution of a nonionic alcoholethoxylate to first determine the exact cloud point and secondly todetermine the other phases that are inherent to the alcohol ethoxylate.This is accomplished by use of the dipping probe instrument, whichmeasures the turbidity change in the ethoxylate as the temperature isincreased from room temperature to ninety (90)° C. Each surfactant willhave its own unique trace or “fingerprint” as the changes of temperatureand turbidity are recorded and noted.

The solubilization rates of hexadecane and 4/1 hexadecane/oleic acidinto 1% solutions were measured at 25° C. using the dipping probecalorimeter system. Hexadecane models a nonpolar lubricating oil while4/1 hexadecane/oleic acid models a polar sebum-like soil. The rates werecalculated by measuring the time required for 10 μl samples of oil tocompletely dissolve into the well-stirred solution as indicated by thedisappearance of turbidity. The results for 4/1 hexadecane/oleic acidare given as an average value for five sequential injections while thedata for hexadecane are based on a single injection.

As shown in the data table, the 7-EO PDO adduct provided fastersolubilization on average than the commercial 7-EO ethoxylate having thesame cloud point temperature. This result was true for both the nonpolarhexadecane oil as well as the nonpolar/polar oil blend containing oleicacid. Rapid solubilization of oil is indicative of good-cleaningsurfactant systems that provide enhanced removal rates of oily soilsfrom various solid substrates.

ACTUAL VALUES Physical Property C₁₂-1 C₁₄-1 C₁₆-1 Attributes N25-7 PDO7EO PDO 7EO PDO 7EO Cloud Point UP (° C.) 52.6 53.6 47 42.7 DOWN (° C.)53.4 53.7 47.7 43 AVERAGE (° C.) 53.0 53.7 47.4 42.9 L α Phase (° C.range) 91-86 72.6-79   71-82 Short @ 70 L Phase (° C. range) —   83-85.986.5-88.4 ˜80 L₂ Phase (° C. range) — — — double cloud Solubilizations*(μL/minute) 4/1 Hexadecane/oleic acid 10 μL 50.0 200.0 26.7 0.2 10 μL40.0 66.7 20.0 0.2 10 μL 28.6 40.0 20.0 None 10 μL 28.6 28.6 33.3 None10 μL 20.0 20.0 11.4 None Average 33.4 71.1 22.3 0.2 Hexadecane 10 μL0.083 0.333 0.089 0.064 10 μL None None None None 10 μL None None NoneNone *25° C. Solubility

Solubility Key Result Time, Min. Seconds 100 0.1 6 50 0.2 12 5 2 120 0.520 1200 0.05 200 12000

1. An alcohol alkoxysulfate composition comprising an alcohol alkoxysulfate represented by the formula:

wherein R₁ represents hydrogen or a hydrocarbyl group having from 1 to 3carbon atoms, R₂ represents a hydrocarbyl group having from 1 to 7carbon atoms, x is a number ranging from 0 to 16, A is an alkylene grouphaving carbon number in the range of 2 to 4, y is a number ranging from1 to 9, wherein the total number of carbon atoms in the alcoholalkoxysulfate excluding A ranges from 9 to 24, and M is hydrogen or acation.
 2. The alcohol alkoxysulfate composition of claim 1 wherein A isan alkylene group having carbon number in the range of 2 to
 3. 3. Thealcohol alkoxysulfate composition of claim 2 wherein A is an alkylenegroup having carbon number of
 2. 4. The alcohol alkoxysulfatecomposition of claim 1 wherein M is hydrogen.
 5. The alcoholalkoxysulfate composition of claim 1 wherein M is a cation effective toprovide a water soluble alkyl ether sulfate composition.
 6. The alcoholalkoxysulfate composition of claim 5 wherein M is selected from thegroup consisting of ammonium, alkanolammonium, monovalent metal cations,and polyvalent metal cations.
 7. The alcohol alkoxysulfate compositionof claim 1 wherein R₂ is a hydrocarbyl group having 1 carbon atom. 8.The alcohol alkoxysulfate composition of claim 7 wherein R₁ is hydrogen.9. The alcohol alkoxysulfate composition of claim 1 wherein x is anumber ranging from 3 to
 13. 10. The alcohol alkoxysulfate compositionof claim 3 wherein R₂ is a hydrocarbyl group having 1 carbon atom. 11.The alcohol alkoxysulfate composition of claim 10 wherein R₁ ishydrogen.
 12. The alcohol alkoxysulfate composition of claim 3 wherein xis a number ranging from 3 to
 13. 13. A detergent composition comprisingthe alcohol ethoxysulfate composition of claim
 1. 14. A detergentcomposition comprising the alcohol ethoxysulfate composition of claim 3.15. A detergent composition comprising the alcohol ethoxysulfatecomposition of claim
 5. 16. A detergent composition comprising thealcohol ethoxysulfate composition of claim
 7. 17. A detergentcomposition comprising the alcohol ethoxysulfate composition of claim 9.